Process for improving fibrous material and the material treated by such process



Patented Feb. 20, 1945 UNITED STATES PATENT OFFICE PROCESS FOR IMPROVINGFIBROUS MATE- RIAL AND THE MATERIAL TREATED BY SUCH PROCESS CharlesGraenachcr, Riehen,

Richard Sallmann,

Bottmingen, Otto Albrecht, Muenchenstein, and

Just Frei, Basel,

Switzerland, assignors to Society of Chemical Industry in Basic, Basel,

Switzerland No Drawing. Application January 15, 1940, Se-

rial No. 314,008.

6 Claims. This application is a continuation-in-part of In SwitzerlandMay 31, 1938 our application Serial No. 276,026, flied May 26,

wherein R represents an organic radical containing less than carbonatoms and at least one hydrogen halide ester group, R1 and R2 stand for'a member of the group consisting of hydrogen,

lower alkyl and halogen substituted lower allgvl,

x stands for a member of the group consisting of oxygen, sulfur and acarboxylic acid amide bridge, and y stands for a basic group whichdetermines the solubility of the product in water "and is united withthe CH2- group by a heteroatom, and heating the thus treated materials.In this manner a textile material of basic character or enhanced basiccharacter is produced. R of the above formula may be a hydrocarbonradical, for instance methyl, ethyl, propyl, octyl, decyl, substituted,if desired, by hydroxy groups or the like, or a hydrocarbon chaininterrupted by hetero-atoms, such as oxygen or sulfur. Hydrogen halideester groups include such halogen atoms, for instance chlorine orbromine atoms, which by reaction of alcoholic hydroxyl groups withhydrogen halides may be introduced into organic compounds under suitableconditions. Halogenatoms which are hydrogen halide esters aredistinguished from other halogen atoms which are not such esters, forexample the halogen atoms in the acid halides, by the property of beingconverted into basic groups when heated with basic compounds.Particularly suitable are such products in which the hydrogen halideester group is linked to that carbon atom of the radical R which isbound to the group This is the case for example with the products of theformulas w OH-CHr-CH-CHa-O-CHr-N-CH:

l 1 CH;

The products of the last four formulas illustrate the formula amidebridge, is for example the product of the formula By the expressionhetero-atom there are to be understood as usual such atoms which aredifierent from carbon atoms and which may be a member of a hetero-cycle,as is the case with oxygen,

sulfur or nitrogen.

Basic groups which determine the solubility of the products in water arefor example amino or imino groups. for example in the form of thiourearadicals, ammonium groups such as quaternary ammonium groups or ternarysulfonium groups.

Further products which may be used in this invention and correspond withthe general formula prises at least one halogen atom, for example fromethylene-chlorhydrin, 3-chloropropanol-- (1) :3-dichloropropano1-(1),2-chloro-2-methylpropanol-(l) by reaction with formaldehyde and halogenhydride.

Further products which may be used in this invention and correspond withthe general formula wherein R, R1, R: and u have the significance givenabove and :c is a carboxylic acid amide bridge, may be obtained in theknown manner from halogenated carboxylic acid amides such aschloracetamide, ,S-chloropropionic acid amide, a-bromobutyric acidamide, a-bromolauric acid amide, a-bromostearic acid amide,2:9:10-tribromostearic acidamide, chlorosuccinic acid diamide,para-chloromethyl-benzamide, naphthenic acid amides and resin acidamides which contain halogen atoms capable of exchange by means offormaldehyde and a salt of a tertiary amine. Alternatively theN-methylolcarboxylic acid amide obtainable from the carboxylic acidamide in the known manner may be caused to react with a salt or additionproduct of the tertiary amine preferably in presence of a free tertiaryamine to form a quaternary ammonium salt.

As products of the general formula wherein R, R1, R2 and a: have thesignificance given above and y is the residue of a thio-urea there maybe used those which are obtainable from a-halogenmethylethers,a-halogenmethylthioethers, N-halogenmethylamides or N-methylolamides ofcarboxylic acids and thio-ureas, such as thio-urea itself. Methods forthe production of such thio-urea derivatives from carboxylic acid amidesare described, for instance, in application Serial No. 251,848, filedJanuary 19, 1939, now Patent No. 2,345,109.

The products which are to be used according to the present invention maybe caused to act on textile materials preferably by impregnating thematerial with a solution or dispersion of the product. if desired inpresence of a catalyst. for

instance a weak acid or acid salt and subsequent treatment at a raisedtemperature, for instance 115-120 C. As solvent or dispersing agentwater is best, especially in the case of products of low molecularweight. However, other organic solvents, for instance pyridine,dimethylaniline or dioxane may be used. Where a dispersion is necessarythis can be made by known methods.

Textile materials treated according to the present invention may betreated afterwards with ammonia, a primary, secondary or tertiary aminesuch as methylamine, monoethanolamine, diethanolamine, trimethylamine,triethylamine, triethanolamine, pyridine or dimethylaniline; reactionmay occur in the known manner at an ordinary or raised temperature.

When treating fibrous materials with the products of the general formulaas defined above, for instance products of the formula R-CHP:cCHr-y inthe heat there are formed basic fibrous materials. In all probabilitythe basic group 1/ enters into reaction on heating with the hydrogenhalide ester groups present in the radical R. whereby reaction productsof the compounds used which may contain only basic groups in stableunion are fixed on the fibrous materials in a form which is fast towashing. Tertiary amines eliminated, for instance from quaternaryammonium groups by the heat-treatment are in all probabilitysubsequently bound by the reactive halogen atoms with formation of newquaternary ammonium groups.

The basic fibrous materials, obtainable according to the presentinvention, especially from cellulose material or material containingcellulose may be dyed deep fast tints with acid dyestuffs such as acidwool dyestuffs or acid dyestuffs containing metal in complex union,mordant dyestuffs, sulfuric acid estersalts of vat dyestuffs. dyestuffesters or amides such as are described in U. S. Patent 2,095,600 and inpatent application Serial No. 173.528, filed November 8, 1937.. nowPatent No. 2,235,480. Dyestuif intermediate products of acid characterare also absorbed by the textile materials containing basic groups.Direct dyestuffs yield for example on basic cellulose derivatives,obtainable by the process of the invention, dyei-ngs which in generalare more fast to washing than those obtained on the untreated material;this is probably due to the formation of a salt. The acid dyestufi takenup by the basic cellulose derivative can, if its constitution permits,be diazotized on the fiber and de' veloped in the usual manner with anazo-component. It is also possible to treat a suitable dyestufi on thefiber with a diazonium compound.

Similarly to the acid dyestuffs and their intermediate products othercompounds of an acid nature, for instance fatty acids, resin acids,naphthenic acids, sulfuric acid esters of alcohols of high molecularweight or of hydroxy-fatty acids and their esters, also sulfonic acidsof high molecular weight which contain besides an aliphatic orcycloaliphatic radical of high molecular weight an external sulfonicacid group, for instance cetyl-sulfonic acid, oleyloxyethane-sulfonicacid, N-oleyl-N-methyl-aminoethane sulfonic acid, N-benzyl-/i-heptadecylbenzimidazoldisulfonic acid.

sulfophthalic acid-mono-octadecylester and salts of these acids may beabsorbed by the textile material containing the basic groups. inparticular the basic cellulose derivatives. By suitable choice of thecomponents there may be obtainedin this manner a surprisingly soft feelof the goods.

By the application of the process to textile materials such as wool andsilk which already contain basic groups, the basic character of thematerial may be increased.

In case the process of the invention is applied to colored textilegoods, there is the possibility of enhancing the fastness of the dyeingsespecially the fastness to washing. These dyeings which have beenobtained with dyestuffs forming colored anions like dyestuffs containingsulfo-groups whether these dyestuffs are for instance acid wooldyestuffs or direct cotton dyestuffs are improved by treatment with theproducts of the kind in question. The products to be used in theinvention are soluble in water or easily dispersed therein and may bedecomposed by heat or by treatment with saponifying agents whereuponthey separate as insoluble bodies. If this decomposition occurs on thesubstratum, for int stance a textile, the insoluble body separates in anadherent form. It ma impart, according to its nature, valuableproperties to the fiber. Among these may be mentioned the waterproof orwater-repellent character fast to washing which in some cases isconnected with an especial softness and fullness. which latter may bestill further enhanced by addition of a suitable filling agent.

There may be also a considerable diminution of the hygroscopic characterand an increase of insulating properties with reference to heat andelectricity. As further properties which can he imparted to the fiberthere may be named the prevention of the tendency to crease, preventionof the shifting of the threads, diminution of lustre, increase ofstability to water. prevention of shrinking of the fabric and in thecase of wool the prevention of felting. By local application of theprocess, calendering effects, matte effects and damask effect may beproduced and also color effects which have their origin in the changedaffinity of the fiber to dyestuffs. Whenthe process is applied tocolored textiles the properties of the dyeings such as fastness tolight, to rubbing. to washing and to water are essentially increased.These different effects may be interconnected.

The process is applicable to vegetable and animal fibrous material or tofibrous artificial products, for instance cellulose or.materialscontaining a cellulose. cotton, viscose artificial silk, copperartificial silk, paper. wool, silk and mixed fibrous materials, forinstance in the form of threads or fabrics. Moreover materials ofartificial fibers which contain cellulose or cellulose derivatives orprotein substances may be treated.

The products used for the process of the invention may be used alone ortogether w th other materials. for instance salts. especially those offeeble acid, for instance sodium acetate and together with solvents.soapy substances and protective colloids may be used as dressing,weighting and softening or matting agents.

The following examples illustrate the invention, the relationship ofparts by weight to parts by volume is that which exists between the kiloand the liter.

Example 1 Cotton fabric is impregnated with an aqueous solution of 8-10per cent strength of the fi-chlorethoxymethylpyridinium chloridecorresponding to the formula c1-oHioinocuii at 30-40 C. with addition ofsodium acetate; it is then squeezed, dried and heated for 1-2 hours at-125 C. The material thus obtained and lightly rinsed shows a pronouncedaffinity for acid wool dyestuffs. This property may be somewhatincreased if the material after it has been heated is treated with abase, for instance, pyridine. trimethylamine or piperazine.

- Instead of the above used product there may also be used the productsobtainable in analogous manner from 1:2 propyleneglycolchlorohydrine, l:3-propyleneglycolchlorohydrine, butyleneglycolchlorohydrine,hexyleneglycolchlorohydrine. glycerine-B-mono-chloi'ohydrine.

Example 2 Textile goods, for example cotton fabric, are treated in themanner described in Example 1 with a solution of thechloracetaminomethylpyridinium chloride. obtainable frommethylolchloracetamide and pyridine hydrochloride correspond ng to theformula \NH-CH2N' \rzn- By this treatment the material acquires apronounced afllnity for acid wool dyestuffs.

The chloracetaminomethy lpyridinium chloride may be obtained as follows:

12.3 parts of methylolchloracetamide are dissolved in 50 parts by volumeof alcohol and after an addition of 12 parts of pyridine-hydrochloridethe whole is boiled for one hour under reflux. After distilling thealcohol the new quaternary pyridinium chloride remains in the form of anamorphous colorless mass freely soluble in water; after standing forsome time the mass becomes a crystall ne powder.

Instead of the above quaternary salt there may also be used suchproducts which are derived in analogous manner from the,Bchloropropionic acid amide or from the cz-blOlTlOVSJBliC acid amide.

Example 3 A cotton fabric which has been dyed with 2 2 per cent of itsweight of Direct Fast Violet 2RL (Schultz, Farbstofitabellen, 7th editon. vol. II. page 88) and is then treated with a solution of 10 per centstrength of fi-chlorethoxymethylpyrL dinium chloride corresponding tothe formula in presence of an equivalent quantity of sodium acetate for10 minutes at 20-30" C.; it is then squeezed and dried preferably at. alow temperature and then heated for 1-2 hours at 115-120 C. The dyeingthus treated has a pronounced fastness to water and to washing.

Example 4 Cotton fabric is treated asfollows with the condensationproduct from achlorethyl-chlormethylether corresponding probably to theformula.

2 parts of the condensation product from chloromethyl-p-chloroethyletherand thiourea are dissolved in 4 parts of distilled water. After additionof 14 parts by volume of a sodium acetate solution of per cent strengtha piece of bleached cotton fabric is impregnated in this solution,squeezed, dried at 50 C. and then heated for 10 minutes to 120 C. Thematerial is rinsed in hot water, dried and heated in pyridine during 30minutes to 100 C. After washing out and drying the cotton fabric thustreated has a good amnity for wool dyestuffs.

The condensation product used can be prepared as follows:

A solution of 12.8 parts of chloromethyl-fl-chloroethylether in 30 cc.of dry acetone is added in drops, while cooling with ice and stirring,to a suspension of 8.5 parts of finely pulverized thiourea in 40 cc. ofdry acetone. When all is introduced stirring is continued for a furtherhour at wherein R represents an organic radical containing at least onehydrogen halide ester group, R1 and R2 stand for a member of the groupconsisting of hydrogen, lower alkyl and halogen substituted lower alkyl,:1: stands for a member of the group consisting of oxygen, sulfur and acarboxylic acid amide bridge, and y stands for a member of the groupconsisting of quaternary ammonium groups and isothiourea radicals insalt form united with the --CH: group by their sulfur atom, drying thematerials thus treated, and

heating them to at least 100f C.

2. A process for improving fibrous materials, which comprises treatingthe materials with a product of the general formula wherein R representsan alkyl radi al cont in n less than 5 carbon atoms and at least onehydrogen halide ester group bound to that carbon atom of the radical Rwhich unites the radical R with the --CH2 group, q stands for aquaternary nitrogen atom, and 2 stands for a monovalent anion, dryin thematerials thus treated and heating them to at least C.

3, A process for improving fibrous materials. which comprises treatingthe materials with a product of the formula drying the materials thustreated, and heatin them to at least 100 C.

4. Fibrous materials treated at temperatures of at least 100 C. afterprevious drying with a product of the general formula wherein Rrepresents an organic radical containing at least one hydrogen halideester group, R1 and R: stand for a member of the group cons sting ofhydrogen, lower alkyl, and halogen substituted lower alkyl, and 1!stands for a member of the group consisting of quaternary ammoniumgroups and isothiourea radicals in salt form united with the CH2-- groupby their sulfur atom, which fibrous materials have basic properties.

5. Fibrous materials treated at temperatures oi. at least 100 C. afterprevious drying with a product of the general formula wherein Rrepresents an alkyl radical containing less than 5 carbon atoms and atleast one hydrogen halide ester group bound to that carbon atom of theradical R which unites the radical R with the CH2 group, q stands for aquaternary nitrogen atom, and 2 stands for a monovalent anion, whichfibrous materials have basic properties.

6. Fibrous materials treated at temperatures of at least 100 C. afterprevious drying with a product of the formula which fibrous materialshave basic properties.

CHARLES GRAENACHER. RICHARD SALLMANN. OTTO ALBRECHT. JOS'I FREI.

